Non-Heme-Iron-Mediated Selective Halogenation of Unactivated Carbon-Hydrogen Bonds.

ABSTRACT: Oxidation of the iron(II) precursor [(L¹ )Fe^II Cl₂ ], where L¹ is a tetradentate bispidine, with soluble iodosylbenzene (^s PhIO) leads to the extremely reactive ferryl oxidant [(L¹ )(Cl)Fe^IV =O]⁺ with a cis disposition of the chlorido and oxido coligands, as observed in non-heme halogenase enzymes. Experimental data indicate that, with cyclohexane as substrate, there is selective formation of chlorocyclohexane, the halogenation being initiated by C-H abstraction and the result of a rebound of the ensuing radical to an iron-bound Cl^- . The time-resolved formation of the halogenation product indicates that this primarily results from ^s PhIO oxidation of an initially formed oxido-brid

SUBMITTER: Bleher K 

PROVIDER: S-EPMC9300152 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature